US4481244A - Material used to bear writing or printing - Google Patents

Material used to bear writing or printing Download PDF

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Publication number
US4481244A
US4481244A US06/459,987 US45998783A US4481244A US 4481244 A US4481244 A US 4481244A US 45998783 A US45998783 A US 45998783A US 4481244 A US4481244 A US 4481244A
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United States
Prior art keywords
ink
parts
sample
polymer
coating
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Expired - Lifetime
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US06/459,987
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English (en)
Inventor
Masahiro Haruta
Takashi Hamamoto
Shigeo Toganoh
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Canon Inc
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Canon Inc
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Priority claimed from JP1616382A external-priority patent/JPS58134784A/ja
Priority claimed from JP57016161A external-priority patent/JPS58132586A/ja
Priority claimed from JP1616682A external-priority patent/JPS58134787A/ja
Priority claimed from JP57016159A external-priority patent/JPS58132584A/ja
Priority claimed from JP1616482A external-priority patent/JPS58134785A/ja
Priority claimed from JP57016162A external-priority patent/JPS58134783A/ja
Priority claimed from JP1616582A external-priority patent/JPS58134786A/ja
Priority claimed from JP1616082A external-priority patent/JPS58132585A/ja
Application filed by Canon Inc filed Critical Canon Inc
Assigned to CANON KABUSHIKI KAISHA, A CORP. OF JAPAN reassignment CANON KABUSHIKI KAISHA, A CORP. OF JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HAMAMOTO, TAKASHI, HARUTA, MASAHIRO, TOGANOH, SHIGEO
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/508—Supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249981—Plural void-containing components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate

Definitions

  • the present invention relates to materials on which images such as letters and figures are to be written or printed with a recording liquid.
  • the materials are simply referred to as recording materials or recording paper.
  • the ink-jet recording system makes a record by forming ink droplets with any of various ink-jetting processes (e.g. electrostatic attractive process, mechanical vibration or displacement process by use of piezoelements, bubbling process where bubbles are generated by impulsive heating, etc.), and leading parts or all of the droplets to adhere onto recording material such as paper.
  • various ink-jetting processes e.g. electrostatic attractive process, mechanical vibration or displacement process by use of piezoelements, bubbling process where bubbles are generated by impulsive heating, etc.
  • ink is generally required not to blot on recording paper so that the printed letters or figures may not become obscure.
  • the ink is also desired to dry so quickly as to prevent the recording paper from incidental staining with undried ink, and the coloring matter of ink fixed on the paper is desired not to fade out as long as possible.
  • the ink-jet recording system should satisfy the following requirements:
  • An ink dot when overlapping a previously applied ink dot, does not disorder or diffuse it particularly in multicolor or full-color recording.
  • Ink dots do not diffuse on recording paper so as not to be enlarged more than needs.
  • Ink dots have high optical density and distinct perimeter lines.
  • Recording paper has a high whiteness and a good contrast to ink dots.
  • the primary object of this invention is to solve the above problems unsolved by the prior art in the present technical field, in particular to provide a high performance recording paper which fulfills almost all the above-cited requirements in the recording with liquid ink by means of writing tools or ink-jet recording systems.
  • a material used to bear writing or printing which comprises a substrate and a coating layer formed thereon from a coating material containing a polymer having both hydrophilic segments and hydrophobic segments.
  • FIGS. 1 and 2 are illustrations outlining the structure of the recording paper of this invention.
  • FIGS. 3-7 are traced copies of electron microscopic photographs of coating faces of present recording paper samples.
  • numeral 1 represents the liquid-absorption substrate constituted of a porous material, as paper or cloth, or a plastic film or sheet.
  • Numeral 2 represents the coating layer, which receives ink.
  • the coating layer 2 is basically formed from a film-formable coating material containing mainly a polymer having both hydrophilic segments and hydrophobic segments.
  • the coating material may mainly contain both a porous inorganic powder and a polymer having hydrophilic segments along with hydrophobic segments. Further, the coating material may mainly contain a polymer having both hydrophilic segments and hydrophobic and dye-attracting segments. Alternatively, the coating material may mainly contain both a porous inorganic powder and a polymer having hydrophilic segments along with hydrophobic and dye-attracting segments.
  • Such a polymer can be prepared chiefly from addition-polymerizable vinylic monomers.
  • Hydrophilic segments comprising carboxyl or sulfo groups, or ester groups thereof are introduced in the polymer by using a prescribed amount of an ⁇ , ⁇ -unsaturated monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, an itaconic acid monoester, maleic acid, a maleic acid monoester, fumaric acid, a fumaric acid monoester, vinylsulfonic acid, sulfoethyl methacrylate, sulfopropyl methacrylate, or sulfonated vinylnaphthalene.
  • an ⁇ , ⁇ -unsaturated monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, an itaconic acid monoester, maleic acid, a maleic acid monoester, fumaric acid, a fumaric acid monoest
  • monomers most suitable for introducing the hydrophobic segments are styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, and esters derived from aliphatic C 8 -C 18 aliphatic alcohols and ⁇ , ⁇ -ethylenic unsaturated carboxylic acids.
  • the following monomers can be used for the same purpose: acrylonitrile, vinylidene chloride, ⁇ , ⁇ -ethylenic unsaturated carboxylic acid esters other than the above esters, vinyl acetate, vinyl chloride, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide, and the like.
  • Monomers most suitable for introducing the hydrophobic and dye-attracting segments are, for example, acrylonitrile, vinylidene chloride, ⁇ , ⁇ -ethylenic unsaturated carboxylic acid esters, vinyl acetate, vinly chloride, arylamide, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide, and the like.
  • styrene styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, and esters derived from aliphatic C 8 -C 18 alcohol and ⁇ , ⁇ -ethylenic unsaturated carboxylic acids.
  • a salt of the polymer prepared from a combination of the above-cited monomers for the purpose of making the polymer soluble or colloidally dispersible in the medium of the coating material.
  • Substances combined with the polymer to form the salt include alkali metals such as Na and K; aliphatic amines such as mono-, di-, and tri-methylamines and mono-, di-, and tri-ethylamines; alcoholamines such as mono-, di-, and tri-ethanolamines, mono-, di-, tri-propanolamines, methylethanolamine, and dimethylethanolamine; and morpholine and N-methylmorpholine.
  • a particularly important factor in the present polymer is the proportion of monomer units constituting the hydrophilic segments.
  • the content of monomer units containing carboxyl group or sulfo group, or ester group thereof, which constitute the hydrophilic segments exceeds about 40% by weight of the polymer, the so-called sizing effect of the polymer on the substrate 1 is lowered and thereby the ink applied onto the coating layer 2 will blot thereon too much.
  • the color density of ink fixed is low in this case because the concentration of color-adsorbing sites decreases.
  • the content of hydrophilic monomer units less than 2% by weight lowers the binding force between the coating layer 2 and the substrate 1 making the coating layer 2 readily peelable.
  • the content of hydrophilic monomer units is preferably about 25 to 40% by weight.
  • the molecular weight of the polymer is desired to be at least about 2000 since the lower molecular weight deteriorate the film-forming property.
  • the polymer can be prepared, for instance, in the following way: Essential monomers are mixed in a prescribed ratio and polymerized to a desired molecular weight by a polymerization process such as solution polymerization, emulsion polymerization, or suspension polymerization using a polymerization regulator if necessary.
  • a polymerization process such as solution polymerization, emulsion polymerization, or suspension polymerization using a polymerization regulator if necessary.
  • Another acceptable process comprises preparing in the first place a polymer containing acid anhydride, ester, nitrile, or hydroxyl groups, followed by hydrolysis, esterification, sulfate-esterification, or sulfonation of these group, thereby forming hydrophilic groups, such as carboxyl and sulfo groups, in the polymer.
  • the polymer in the form of amine salt may be prepared in any step of the polymer synthesis; for instance, it may be prepared by polymerizing monomer mixtures containing an amine salt of ⁇ , ⁇ -unsaturated carboxylic acid or adding an amine after polymerization or hydrolysis as mentioned above.
  • one or more of the polymers synthesized as described above are dissolved or dispersed in a solvent to prepare the coating material.
  • the binding resin may be water-soluble or organic solvent-soluble.
  • Water-soluble resins suitable for this purpose include poly(vinyl alcohol), starch, casein, gum arabic, gelatin, polyacrylamide, carboxymethylcellulose, sodium polyacrylate, and sodium alginate.
  • Organic solvent-soluble resins suitable include poly(vinyl butyral), poly(vinyl chloride), poly(vinyl acetate), polyacrylonitrile, poly(methyl methacrylate), poly(vinyl formal), melamine resins, polyamide resins, phenolic resins, polyurethane resins, and alkyd resins.
  • Solvents suitable for the coating material are water and mixtures of water with water-miscible organic solvents.
  • the water-miscible solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; ketones or ketoalcohols such as acetone, methyl ethyyl ketone, and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; esters such as ethylene carbonate and propylene carbonate; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and diethanolamine.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutan
  • porous inorganic particles used jointly with the above-mentioned polymer in the coating material are primarily intended, in this invention, for physical adsorption and capture of the coloring matter (e.g., dye) of the ink applied onto the coating layer 2.
  • Materials effectively used for this purpose are white porous inorganic pigments having an ionic property on the particle surface.
  • Such pigments include natural zeolites, synthetic zeolites (e.g., molecular sieves mfd.
  • one or more kinds of these inorganic particles are dispersed in the coating solvent along with one or more of the above-mentioned polymers dissolved or dispersed.
  • the coating layer 2 can be formed by applying the coating material onto the substrate 1 in a known coating way (e.g., roll coating, rod bar coating, spray coating, or the like) so as to give a dry coating weight generally of ca.1-10 g/m 2 , preferably of ca.2-5 g/m 2 from a more practical aspect. The coating material is then dried as soon as possible.
  • a known coating way e.g., roll coating, rod bar coating, spray coating, or the like
  • the coloring matter e.g., dye
  • the coloring matter e.g., dye
  • each scale-like lamellae 3 are not particularly limited but approximately 10 ⁇ 10 ⁇ to hundreds ⁇ hundreds ⁇ in general.
  • the width of each micro-crack 4 is also not particularly limited but usually several ⁇ .
  • the dimensions or geometry of the scale-like lamellae 3 and the widths of the micro-cracks 4 can be varied at will within the above respective ranges by regulating or controlling the composition of the coating material and the film-forming conditions, in particular the drying conditions after coating.
  • the coloring matter (e.g., dye) of the ink is selectively adsorbed and captured in the scale-like lamellae 3 by forming ionic bonds or hydrogen bonds, or the like with the polymer and physical bonds with the porous inorganic particles, while the solvent of the ink passes through the micro-cracks 4 and is quickly absorbed into the substrate 1.
  • the coloring matter of ink, on recording is mostly captured by the upper-most zone of recording paper, so that excellent coloration of the applied ink is obtainable.
  • the solvent of the ink rapidly moves through the micro-cracks to the under-lying substrate, so that the ink on the paper surface is rapidly brought into an apparently dry state.
  • the scale-like lamellae 3 are particularly effective in preventing the applied ink dots from being enlarged more than needs or from being dim at the perimeters, thus giving ink dots of high optical density. This is caused by the intensive adsorption of the coloring matter of ink in the scale-like lamellae 3.
  • the power of this adsorption principally depends upon chemical properties of the polymer (e.g., the ionic character) and physical properties of the inorganic particles (e.g., the voids).
  • the surface area occupied by the scale-like malellae 3 of the whole surface area of recording paper is excessively small, in other words, the surface area occupied by the micro-cracks 4 is extremely large.
  • the efficiency of capturing the coloring matter is lowered, resulting in a poor coloration or low optical density of ink dots; the amount of ink migrating to the substrate 1 increases, giving rise to a so-called back penetration phenomenon of ink; and the shapes of ink dots become worse. Accordingly, the conditions leading to such a state of the coating layer should be avoided.
  • Samples of the polymer, a main component of the coating layer in this invention, used in the Examples were prepared as shown in the following Preparation Examples or were the commercial ones shown below: In the Examples and Preparation Examples, "parts" means parts by weight.
  • a mixture of water (50 parts), isopropanol (30 parts), sodium dodecylbenzenesulfonate (0.5 part), and ammonium persulfate (0.5 part) was heated to 60° C. in a four-necked separable flask equipped with a stirrer and a dropping funnel.
  • a mixture of styrene (5 parts), acrylic acid (9 parts), and butyl acrylate (5 parts) was added dropwise thereto from the dropping funnel over 60 minutes. After completion of the addition, the temperature was raised to 80° C. and the polymerization was conducted for 2 hours with stirring.
  • the molecular weight of the polymer obtained was about 50,000.
  • Methyl methacrylate (8 parts), styrene (5 parts), itaconic acid (15 parts), benzoyl peroxide (1 part), lauryl mercaptan (1 part), diacetone alcohol (50 parts), and ethylene glycol (20 parts) were charged in the same flask as used in Preparation Example 1. The polymerization was conducted for 6 hours under a stream of nitrogen. The molecular weight of the polymer obtained was about 30,000.
  • a coating material (usually in slurry form) for forming the coating layer was applied to coat one side of base paper so as to give a dry coating weight of approximately 4 g/m 2 .
  • the optical density of ink dot of the characteristics was determined by using a microdensitometer (PDM-5, mfd. by Konishiroku Photographic Ind. Co., Ltd.) with a 30 ⁇ 30 ⁇ slit at a recorded sample speed of 10 ⁇ /sec. in the x-axial direction and a chart speed of 1 mm/sec (speed ratio of sample to chart: 1/100).
  • PDM-5 microdensitometer
  • the diameter of ink dots were measured by use of a microscope.
  • the fixation time for ink of the characteristics is the time passed from the application of an ink droplet onto a sample paper until the ink comes not to adhere to the surface of a rubber press roll placed at a definite position apart in the sample-forwarding direction from the ink-jetting head used; said time was determined by varying the sample speed, in other words, varying the time passed from the application of ink dot until the ink dot contacts with the rubber roll.
  • the diameter of ink-jetting orifice of the ink-jetting head used was 50 ⁇ .
  • compositions were thoroughly stirring and mixed severally to prepared five kinds of slurry:
  • composition A Composition A
  • Viscosity 3.8 cps., as measured with a rotation viscometer (E-type, mfd. by Tokyo Keiki Co., Ltd.).
  • a slurry was prepared by thorough stirring and mixing the polymer (100 parts) obtained in Preparation Example 3, water (110 parts), and ethanol (50 parts). The slurry was applied onto base paper (basis weight 65 g/m 2 ) and dried under the same conditions as in Example 1 to prepare a recording paper sample.
  • a slurry was prepared by thorough stirring and mixing the polymer (100 parts) obtained in Preparation Example 1 and water (150 parts). The slurry was applied onto base paper (basis weight 60 g/m 2 ) and dried under the following five different conditions to prepare Samples VI-X of recording paper.
  • Sample VI Natural drying by leaving the specimen standing.
  • Sample VII In a 60° C. oven for 2 hours.
  • Sample VIII In a stream of 90° C. hot air for 30 minutes.
  • Sample IX In a stream of 110° C. hot air for 1 minute.
  • Sample X In a stream of 180° C. hot air for 2 seconds.
  • Electron microscopic photographs (magnification factor 200) of coating faces of the samples are shown by FIGS. 3-7.
  • a slurry was prepared by thorough stirring and mixing the polymer (100 parts) obtained in Preparation Example 3, water (110 parts), and ethanol (50 parts). The slurry was applied onto base paper (basis weight 65 g/m 2 ) and dried in a stream of 180° C. hot air for a few seconds to prepare a sample of recording paper.
  • Electron microscopic photographs of the coating surface exhibited nearly the appearance as shown by FIG. 7.
  • a slurry was prepared by thorough stirring and mixing the polymer (80 parts) obtained in Preparation Example 6, a poly(vinyl alcohol) (20 parts), and water (150 parts). Then, a sample of recording paper was prepared and tested in the same manner as in Example 8, giving nearly equal results.
  • Example 7 Sample X prepared in Example 7 was tested for ink-jet recording characteristics using the same inks as used in Examples 3 and 4, respectively. The results are shown in Table 4.
  • compositions were thoroughly mixed and ground severally to prepare five kinds of slurry.
  • Synthetic zeolite 80 parts
  • the ink-jet recording tests of this sample gave nearly the same results as in case of Sample XV of Example 14.
  • Example 14 Sample XI of recording paper prepared in Example 14 was tested for the ink-jet recording characteristics using the same inks as used in Examples 3 and 4, respectively. The results are shown in Table 6.
  • a slurry was prepared by thorough stirring and mixing the polymer (30 parts) obtained in Preparation Example 1, a silica powder (50 parts), and water (150 parts). The slurry was applied onto base paper (basis weight 60 g/m 2 ) and dried under the following five different conditions to prepare Samples XVI-XX of recording paper:
  • Sample XVI Natural drying by leaving the specimen standing.
  • Sample XVII In a 60° C. oven for 2 hours.
  • Sample XVIII In a stream of 90° C. hot air for 30 minutes.
  • Sample XIX In a stream of 110° C. hot air for 1 minute.
  • Sample XX In a stream of 180° C. hot air for 2 seconds.
  • Electron microscopic photographs (magnification factor 200) of coating faces of the samples were not much different from those shown in FIGS. 3-7.
  • a slurry prepared by thorough stirring and mixing the polymer (50 parts) obtained in Preparation Example 3, diatomaceous earth (70 parts), and water (110 parts) was applied onto base paper (basis weight 65 g/m 2 ) and dried in a stream of 180° C. hot air for a few seconds to prepare a sample of recording paper.
  • Electron microscopic photographs of the coating surface exhibited nearly the same appearance as shown by FIG. 7.
  • a slurry was prepared by thorough stirring and mixing the polymer (80 parts) obtained in Preparation Example 6, a synthetic zeolite (130 parts), a poly(vinyl alcohol)(20 parts), water (250 parts) and methanol (100 parts). Then, a sample of recording paper was prepared and tested in the same manner as in Example 21, giving nearly equal results.
  • Example 20 Sample XX prepared in Example 20 was tested for the ink-jet recording characteristics using the same inks as used in Examples 3 and 4. The results are shown in Table 8.
  • Example 21 Writing tests by use of a commercial fountain pen were made on the sample of recording paper prepared in Example 21.
  • the sample exhibited quick absorption of ink without ink running thereon, thus very beautiful letters being written.
  • compositions were thoroughly stirring and mixed severally to prepare five kinds of slurry:
  • a slurry was prepared by thorough stirring and mixing the polymer (100 parts) obtained in Preparation Example 6 and water (150 parts). The slurry was applied onto base paper (basis weight 60 g/m 2 ) and dried under the following five different conditions to prepare Samples XXVI-XXX of recording paper.
  • Sample XXVI Natural drying by leaving the specimen standing.
  • Sample XXVII In a 60° C. oven for 2 hours.
  • Sample XXVIII In a stream of 90° C. hot air for 30 minutes.
  • Sample XXIX In a stream of 110° C. hot air for 1 minute.
  • Sample XXX In a stream of 180° C. hot air for 2 seconds.
  • Electron microscopic photographs (magnification factor 200) of coating faces of the samples were not much different from those shown in FIGS. 3-7.
  • Electron microscopic photographs of the coating surface exhibited nearly the same appearance as shown by FIG. 7.
  • a slurry was prepared by thorough stirring and mixing the polymer (80 parts) obtained in Preparation Example 4, a poly(vinyl alcohol) (20 parts), and water (150 parts). Then, a sample of recording paper was prepared and tested in the same manner as in Example 33, giving nearly equal results.
  • Example 33 The sample prepared in Example 33 was tested for the ink-jet recording characteristic using the same inks as used in Examples 3 and 4, respectively. The results are shown in Table 12.
  • Example 33 Writing tests by use of a commercial fountain pen were made on the recording paper prepared in Example 33.
  • the recording paper exhibited quick absorption of ink without ink running thereon, thus very beautiful letters being written.
  • compositions were thoroughly mixed and ground severally to prepare five kinds of slurry.
  • Synthetic zeolite 80 parts
  • a slurry was prepared by thorough stirring and mixing the polymer (30 parts) obtained in Preparation Example 6, a silica powder (50 parts), and water (150 parts) was applied onto base paper (basis weight 60 g/m 2 ) and dried under the following five different conditions to prepare Samples XXXVI-XXXX of recording paper:
  • Sample XXXVI Natural drying by leaving the specimen standing.
  • Sample XXXVII In a 60° C. oven for 2 hours.
  • Sample XXXVIII In a stream of 90° C. hot air for 30 minutes.
  • Sample XXXIX In a stream of 110° C. hot air for 1 minute.
  • Sample XXXX In a stream of 180° C. hot air for 2 seconds.
  • Electron microscopic photographs (magnification factor 200) of coating faces of the samples were not much different from those shown in FIGS. 3-7.
  • a slurry prepared by thorough stirring and mixing the polymer (50 parts) obtained in Preparation Example 3, diatomaceous earth (70 parts), and ethanol (50 parts) was applied onto base paper (65 g/m 2 ) and dried in a stream of 180° C. hot air for a few seconds to prepare a sample of recording paper.
  • Electron microscopic photographs of the coating surface exhibited nearly the same appearance as shown by FIG. 7.
  • a slurry was prepared by thorough mixing the polymer (80 parts) obtained in Preparation Example 4, a synthetic zeolite (130 parts), a poly(vinyl alcohol)(20 parts), water (250 parts) and methanol (100 parts). Then, a sample of recording paper was prepared and tested in the same manner as in Example 45, giving nearly equal results.
  • Example 45 The sample prepared in Example 45 was tested for the ink-jet recording characteristics using the same inks as used in Examples 3 and 4, respectively. The results are shown in Table 16.
  • Example 45 Writing tests by use of a commercial fountain pen were made on the sample of recording paper prepared in Example 45.
  • the sample exhibited quick absorption of ink without ink running thereon, thus very beautiful letters being written.
  • this invention provides recording paper excellent in recording performance characteristics and best suited for multicolor ink-jet recording, particularly in the following respects:
  • the recording liquid (ink) applied onto the recording paper is quickly absorbed thereinto, that is to say, the coloring matter of ink is quickly fixed to the upper zone of the paper and the solvent of ink is also quickly absorbed into the underlying zone of the paper.
  • ink droplets different in color are applied successively in short periods of time to the same point of the paper face, no significant running or blotting of ink occurs thereon, in other words, the spread of ink dots can be inhibited within such an extent as not to impair the clearness of image, and thus good coloration is obtainable.

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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
US06/459,987 1982-02-03 1983-01-21 Material used to bear writing or printing Expired - Lifetime US4481244A (en)

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
JP57016159A JPS58132584A (ja) 1982-02-03 1982-02-03 インクジェット用被記録材
JP57-16166 1982-02-03
JP1616482A JPS58134785A (ja) 1982-02-03 1982-02-03 被記録材
JP57016162A JPS58134783A (ja) 1982-02-03 1982-02-03 インクジェット用被記録材
JP1616382A JPS58134784A (ja) 1982-02-03 1982-02-03 被記録材
JP57-16162 1982-02-03
JP57-16163 1982-02-03
JP57-16160 1982-02-03
JP1616682A JPS58134787A (ja) 1982-02-03 1982-02-03 被記録材
JP1616582A JPS58134786A (ja) 1982-02-03 1982-02-03 被記録材
JP57-16161 1982-02-03
JP57-16159 1982-02-03
JP1616082A JPS58132585A (ja) 1982-02-03 1982-02-03 被記録材
JP57016161A JPS58132586A (ja) 1982-02-03 1982-02-03 インクジェット用被記録材
JP57-16164 1982-02-03
JP57-16165 1982-02-03

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US4544580A (en) * 1982-02-03 1985-10-01 Canon Kabushiki Kaisha Method for recording by writing or printing with ink
US4550053A (en) * 1983-03-24 1985-10-29 Canon Kabushiki Kaisha Recording medium
US4578285A (en) * 1983-03-16 1986-03-25 Polaroid Corporation Ink jet printing substrate
US4636409A (en) * 1983-09-19 1987-01-13 Canon Kabushiki Kaisha Recording medium
US4636410A (en) * 1984-08-29 1987-01-13 Canon Kabushiki Kaisha Recording method
US4636805A (en) * 1984-03-23 1987-01-13 Canon Kabushiki Kaisha Record-bearing member and ink-jet recording method by use thereof
US4678687A (en) * 1984-10-31 1987-07-07 Xerox Corporation Thermal transfer printing sheets containing certain coating compositions thereof
US4686138A (en) * 1985-06-13 1987-08-11 Mitsubishi Paper Mills, Ltd. Direct image offset printing plates
US4721968A (en) * 1983-09-22 1988-01-26 Canon Kabushiki Kaisha Ink jet transparency-mode recorder
US4732786A (en) * 1985-12-17 1988-03-22 James River Corporation Ink jet printable coatings
US4855176A (en) * 1986-12-15 1989-08-08 Kabushiki Kaisha Toyota Chuo Kenkyusho Anti-blurring optical member
US4911977A (en) * 1984-05-25 1990-03-27 Canon Kabushiki Kaisha Recording member
US4956230A (en) * 1987-04-13 1990-09-11 Minnesota Mining And Manufacturing Company Ink receptive transparency sheet
US5039598A (en) * 1989-12-29 1991-08-13 Xerox Corporation Ionographic imaging system
US5073434A (en) * 1989-12-29 1991-12-17 Xerox Corporation Ionographic imaging system
US5139614A (en) * 1991-02-06 1992-08-18 American Cyanamid Company Styrene/acrylic-type polymers for use as surface sizing agents
US5153618A (en) * 1989-12-29 1992-10-06 Xerox Corporation Ionographic imaging system
US5182157A (en) * 1990-11-01 1993-01-26 Van Leer Metallized Products (U.S.A.) Limited Method of forming a coated sheet which wicks away oil and product thereof
US5190805A (en) * 1991-09-20 1993-03-02 Arkwright Incorporated Annotatable ink jet recording media
US5352503A (en) * 1992-09-21 1994-10-04 Rexham Graphics Inc. Recording paper for ink jet recording processes
US5521002A (en) * 1994-01-18 1996-05-28 Kimoto Tech Inc. Matte type ink jet film
US5650473A (en) * 1994-07-22 1997-07-22 National Starch And Chemical Investment Holding Corporation Methods for making styrene copolymers and uses thereof
US5689787A (en) * 1996-05-16 1997-11-18 Eastman Kodak Company Transfer member having sectioned surface coating to enhance micro-compliance
US5834063A (en) * 1995-02-07 1998-11-10 Nisshinbo Industries, Inc. Recording medium and method of producing the same
US5888629A (en) * 1995-10-05 1999-03-30 Azon Corporation Ink jet recording medium
US5888287A (en) * 1997-04-10 1999-03-30 Markem Corporation Washable fabrics ink
US5984454A (en) * 1992-05-25 1999-11-16 Canon Kabushiki Kaisha Image forming system and apparatus constituting the same
US6024441A (en) * 1994-03-09 2000-02-15 Canon Kabushiki Kaisha Image forming apparatus
US6033066A (en) * 1992-01-27 2000-03-07 Canon Kabushiki Kaisha Ink-jet textile printing process
US6116728A (en) * 1992-02-26 2000-09-12 Canon Kabushiki Kaisha Ink jet recording method and apparatus and recorded matter
US6126280A (en) * 1989-03-03 2000-10-03 Fuji Xerox Co., Ltd. Ink recording method
US6153288A (en) * 1997-07-24 2000-11-28 Avery Dennison Corporation Ink-receptive compositions and coated products
US6180238B1 (en) * 1993-03-19 2001-01-30 Xerox Corporation Recording sheets containing oxazole, isooxazole, oxazolidinone, oxazoline salt, morpholine, thiazole, thiazolidine, thiadiazole, and phenothiazine compounds
US6210516B1 (en) 1994-02-18 2001-04-03 Ronald Sinclair Nohr Process of enhanced chemical bonding by electron seam radiation
US6398358B1 (en) 1992-02-26 2002-06-04 Canon Kabushiki Kaisha Textile ink jet recording method with temporary halt function
US6520623B2 (en) * 1995-12-28 2003-02-18 Canon Kabushiki Kaisha Method and apparatus for printing
US20040009312A1 (en) * 2002-06-10 2004-01-15 Koenig Michael F. Waterfast compositions for ink jet recording sheets
US6689421B2 (en) 1998-03-06 2004-02-10 Kodak Polychrome Graphics, Inc. Method of preparing a microporous film, and imaging method
US20040033377A1 (en) * 2002-06-10 2004-02-19 Koenig Michael F. Waterfast dye fixative compositions for ink jet recording sheets
US20040229004A1 (en) * 2003-05-15 2004-11-18 Hazen Paper Company Inkjet receptive and laser printable coating for holographic and metallic media
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US20070125267A1 (en) * 2005-11-01 2007-06-07 Song Jay C Paper substrate having enhanced print density
US20080289786A1 (en) * 2007-05-21 2008-11-27 Koenig Michael F Recording sheet with improved image waterfastness, surface, strength, and runnability
US20090165977A1 (en) * 2007-12-26 2009-07-02 Huang Yan C Paper Substrate containing a wetting agent and having improved print mottle
US20100086709A1 (en) * 2008-10-01 2010-04-08 International Paper Company Paper substrate containing a wetting agent and having improved printability
US20110117359A1 (en) * 2009-11-16 2011-05-19 De Santos Avila Juan M Coating composition, coated article, and related methods
US20110151148A1 (en) * 2009-12-17 2011-06-23 International Paper Company Printable Substrates with Improved Dry Time and Acceptable Print Density by Using Monovalent Salts
US20110151149A1 (en) * 2009-12-17 2011-06-23 International Paper Company Printable Substrates with Improved Brightness from OBAs in Presence of Multivalent Metal Salts
EP2511419A1 (en) 2005-11-01 2012-10-17 International Paper Company A paper substrate having enhanced print density

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JPS60112484A (ja) * 1983-11-24 1985-06-18 Matsushita Electric Ind Co Ltd 像受容体
JPS60122192A (ja) * 1983-12-07 1985-06-29 Matsushita Electric Ind Co Ltd 昇華型感熱記録装置
GB8408079D0 (en) * 1984-03-29 1984-05-10 Ici Plc Inkable sheet
JPS6294379A (ja) * 1985-10-21 1987-04-30 Mitsubishi Yuka Fine Chem Co Ltd 水性インク記録用シ−ト
US4740497A (en) * 1985-12-24 1988-04-26 Eastman Kodak Company Polymeric mixture for dye-receiving element used in thermal dye transfer
WO1988006520A1 (en) * 1987-02-24 1988-09-07 Raychem Corporation A multilayer article having improved printability and mark permanency and a method of making
DE3824012A1 (de) * 1988-07-15 1990-01-18 Nortech Chemie Mit sublimierbaren dispersionsfarbstoffen bedruckten lackbeschichtung, beschichtungsmittel hierfuer und verfahren zur herstellung bedruckter gegenstaende
US5118390A (en) * 1990-08-28 1992-06-02 Kimberly-Clark Corporation Densified tactile imaging paper
GB2277890A (en) * 1993-05-14 1994-11-16 Courtaulds Films Acrylic coatings
DE4425793A1 (de) * 1994-07-21 1996-02-01 Manfred Keppeler Herstellung von Folien und Beschichtungen durch Sprühen
GB2335381B (en) * 1998-03-17 2001-12-12 Ilford Imaging Uk Ltd Ink-jet receiving sheet for oil based inks

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Cited By (73)

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Publication number Priority date Publication date Assignee Title
US4544580A (en) * 1982-02-03 1985-10-01 Canon Kabushiki Kaisha Method for recording by writing or printing with ink
US4578285A (en) * 1983-03-16 1986-03-25 Polaroid Corporation Ink jet printing substrate
US4550053A (en) * 1983-03-24 1985-10-29 Canon Kabushiki Kaisha Recording medium
US4636409A (en) * 1983-09-19 1987-01-13 Canon Kabushiki Kaisha Recording medium
US4721968A (en) * 1983-09-22 1988-01-26 Canon Kabushiki Kaisha Ink jet transparency-mode recorder
US4636805A (en) * 1984-03-23 1987-01-13 Canon Kabushiki Kaisha Record-bearing member and ink-jet recording method by use thereof
US4911977A (en) * 1984-05-25 1990-03-27 Canon Kabushiki Kaisha Recording member
US4636410A (en) * 1984-08-29 1987-01-13 Canon Kabushiki Kaisha Recording method
US4678687A (en) * 1984-10-31 1987-07-07 Xerox Corporation Thermal transfer printing sheets containing certain coating compositions thereof
US4686138A (en) * 1985-06-13 1987-08-11 Mitsubishi Paper Mills, Ltd. Direct image offset printing plates
US4732786A (en) * 1985-12-17 1988-03-22 James River Corporation Ink jet printable coatings
US4855176A (en) * 1986-12-15 1989-08-08 Kabushiki Kaisha Toyota Chuo Kenkyusho Anti-blurring optical member
US4956230A (en) * 1987-04-13 1990-09-11 Minnesota Mining And Manufacturing Company Ink receptive transparency sheet
US6126280A (en) * 1989-03-03 2000-10-03 Fuji Xerox Co., Ltd. Ink recording method
US5073434A (en) * 1989-12-29 1991-12-17 Xerox Corporation Ionographic imaging system
US5153618A (en) * 1989-12-29 1992-10-06 Xerox Corporation Ionographic imaging system
US5039598A (en) * 1989-12-29 1991-08-13 Xerox Corporation Ionographic imaging system
US5182157A (en) * 1990-11-01 1993-01-26 Van Leer Metallized Products (U.S.A.) Limited Method of forming a coated sheet which wicks away oil and product thereof
US5139614A (en) * 1991-02-06 1992-08-18 American Cyanamid Company Styrene/acrylic-type polymers for use as surface sizing agents
US5190805A (en) * 1991-09-20 1993-03-02 Arkwright Incorporated Annotatable ink jet recording media
US6033066A (en) * 1992-01-27 2000-03-07 Canon Kabushiki Kaisha Ink-jet textile printing process
US6116728A (en) * 1992-02-26 2000-09-12 Canon Kabushiki Kaisha Ink jet recording method and apparatus and recorded matter
US6398358B1 (en) 1992-02-26 2002-06-04 Canon Kabushiki Kaisha Textile ink jet recording method with temporary halt function
US5984454A (en) * 1992-05-25 1999-11-16 Canon Kabushiki Kaisha Image forming system and apparatus constituting the same
US5352503A (en) * 1992-09-21 1994-10-04 Rexham Graphics Inc. Recording paper for ink jet recording processes
US6180238B1 (en) * 1993-03-19 2001-01-30 Xerox Corporation Recording sheets containing oxazole, isooxazole, oxazolidinone, oxazoline salt, morpholine, thiazole, thiazolidine, thiadiazole, and phenothiazine compounds
US5521002A (en) * 1994-01-18 1996-05-28 Kimoto Tech Inc. Matte type ink jet film
US6210516B1 (en) 1994-02-18 2001-04-03 Ronald Sinclair Nohr Process of enhanced chemical bonding by electron seam radiation
US6024441A (en) * 1994-03-09 2000-02-15 Canon Kabushiki Kaisha Image forming apparatus
US5886076A (en) * 1994-07-22 1999-03-23 National Starch And Chemical Investment Holding Coporation Methods for making styrene copolymers and uses thereof
US5789511A (en) * 1994-07-22 1998-08-04 National Starch And Chemical Investment Holding Corporation Methods for making styrene copolymers and uses thereof
US5650473A (en) * 1994-07-22 1997-07-22 National Starch And Chemical Investment Holding Corporation Methods for making styrene copolymers and uses thereof
US5834063A (en) * 1995-02-07 1998-11-10 Nisshinbo Industries, Inc. Recording medium and method of producing the same
US5888629A (en) * 1995-10-05 1999-03-30 Azon Corporation Ink jet recording medium
US6520623B2 (en) * 1995-12-28 2003-02-18 Canon Kabushiki Kaisha Method and apparatus for printing
US5689787A (en) * 1996-05-16 1997-11-18 Eastman Kodak Company Transfer member having sectioned surface coating to enhance micro-compliance
US5888287A (en) * 1997-04-10 1999-03-30 Markem Corporation Washable fabrics ink
US6153288A (en) * 1997-07-24 2000-11-28 Avery Dennison Corporation Ink-receptive compositions and coated products
US6689421B2 (en) 1998-03-06 2004-02-10 Kodak Polychrome Graphics, Inc. Method of preparing a microporous film, and imaging method
US20050074601A1 (en) * 2002-03-28 2005-04-07 Seiko Epson Corporation Image protective sheet, image protective solution, inkjet recorded product, and manufacturing method thereof
US20040033377A1 (en) * 2002-06-10 2004-02-19 Koenig Michael F. Waterfast dye fixative compositions for ink jet recording sheets
US20040009312A1 (en) * 2002-06-10 2004-01-15 Koenig Michael F. Waterfast compositions for ink jet recording sheets
US7745525B2 (en) 2002-06-10 2010-06-29 International Paper Company Waterfast dye fixative compositions for ink jet recording sheets
US20110097520A1 (en) * 2002-06-10 2011-04-28 International Paper Company Waterfast dye fixative compositions for ink jet recording sheets
US20090053431A1 (en) * 2002-06-10 2009-02-26 Koenig Michael F Waterfast dye fixative compositions for ink jet recording sheets
US8361573B2 (en) 2002-06-10 2013-01-29 International Paper Company Waterfast dye fixative compositions for ink jet recording sheets
US20040229004A1 (en) * 2003-05-15 2004-11-18 Hazen Paper Company Inkjet receptive and laser printable coating for holographic and metallic media
US20050129880A1 (en) * 2003-05-15 2005-06-16 Hazen Paper Company Inkjet receptive and laser printable coating for holographic and metallic media
US7153554B2 (en) 2003-05-15 2006-12-26 Hazen Paper Company Inkjet receptive and laser printable coating for holographic and metallic media
CN1576457B (zh) * 2003-06-30 2010-05-26 王子制纸株式会社 涂布纸
US7160608B2 (en) 2003-06-30 2007-01-09 Oji Paper Co., Ltd. Coated paper
EP1659219A1 (en) * 2003-06-30 2006-05-24 Oji Paper Company Limited Coated paper
EP1493866A1 (en) * 2003-06-30 2005-01-05 Oji Paper Company Limited Coated paper
US20040265542A1 (en) * 2003-06-30 2004-12-30 Oji Paper Co., Ltd. Coated paper
WO2005068206A1 (en) 2003-12-15 2005-07-28 Sihl Group Ag Porous imaging material
US20070125267A1 (en) * 2005-11-01 2007-06-07 Song Jay C Paper substrate having enhanced print density
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US20080289786A1 (en) * 2007-05-21 2008-11-27 Koenig Michael F Recording sheet with improved image waterfastness, surface, strength, and runnability
US8048267B2 (en) 2007-05-21 2011-11-01 International Paper Company Recording sheet with improved image waterfastness, surface strength, and runnability
US20090165977A1 (en) * 2007-12-26 2009-07-02 Huang Yan C Paper Substrate containing a wetting agent and having improved print mottle
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US20100086709A1 (en) * 2008-10-01 2010-04-08 International Paper Company Paper substrate containing a wetting agent and having improved printability
US20110117359A1 (en) * 2009-11-16 2011-05-19 De Santos Avila Juan M Coating composition, coated article, and related methods
US20110151149A1 (en) * 2009-12-17 2011-06-23 International Paper Company Printable Substrates with Improved Brightness from OBAs in Presence of Multivalent Metal Salts
US20110151148A1 (en) * 2009-12-17 2011-06-23 International Paper Company Printable Substrates with Improved Dry Time and Acceptable Print Density by Using Monovalent Salts
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Also Published As

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GB2116880A (en) 1983-10-05
DE3348367C2 (enrdf_load_stackoverflow) 1992-12-10
US4544580A (en) 1985-10-01
DE3303427C2 (enrdf_load_stackoverflow) 1993-09-16
GB8302071D0 (en) 1983-03-02
DE3303427A1 (de) 1983-08-11
GB2116880B (en) 1985-11-20

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